WO2021064994A1

WO2021064994A1 - Hot-water supply and heating apparatus

Info

Publication number: WO2021064994A1
Application number: PCT/JP2019/039332
Authority: WO
Inventors: 泰光野村; 英治信時; 佐藤　稔
Original assignee: 三菱電機株式会社
Priority date: 2019-10-04
Filing date: 2019-10-04
Publication date: 2021-04-08
Also published as: JP6765573B1; JPWO2021064994A1

Abstract

This hot-water supply and heating apparatus comprises: a fluid circuit that is constituted by a heat source device, pump, and heat storage heat exchanger connected by piping, the heat source device generating heat, the pump applying pressure to a circulating fluid that transports the heat generated by the heat source device, the heat storage heat exchanger dissipating the heat transported by the circulating fluid; a heat storage tank that houses the heat storage heat exchanger, a hot-water supply heat exchanger through which the supply water for hot water supply passes, and a heat storage material that contains a polymer and water, stores the heat from the heat storage heat exchanger, and dissipates the heat into the supply water passing through the hot-water supply heat exchanger; and a water supply pipe that serves as a flow path through which the supply water passes.

Description

Hot water heater

The present invention relates to a hot water supply / heating device. In particular, the present invention relates to a device for supplying hot water by heating water using the heat stored in the heat storage tank.

There is a hot water supply heating device that heats with the heat generated by the heat source machine and can use the generated heat for hot water supply. In hot water supply, the hot water supply / heating device has a configuration in which the heat generated by the heat source machine is stored in the heat storage tank in advance. Then, the hot water supply / heating device heats the water supplied to the hot water supply / heating device with the heat stored in the heat storage tank to supply hot water (see, for example, Patent Document 1). Here, the heat generated by the heat source machine is stored in the heat storage tank by heating water, antifreeze, or the like in the heat storage tank.

Japanese Unexamined Patent Publication No. 2013-174408

As described above, the conventional hot water supply / heating device stores the heat generated by the heat source machine in water or antifreeze in the heat storage tank. The amount of heat stored in the heat storage tank mainly depends on the amount of water or antifreeze filled in the heat storage tank, and the larger the amount of filling, the larger the amount of heat storage. Therefore, in order to increase the amount of heat stored in the heat storage tank, it is necessary to increase the amount of water or antifreeze filled. Therefore, there is a problem that the capacity of the heat storage tank becomes large and large, and the hot water supply / heating device becomes large.

An object of the present invention is to obtain a hot water supply / heating device capable of increasing the amount of heat storage and the amount of heat radiation per volume of a heat storage tank in order to solve the above problems.

In the hot water supply / heating device according to the present invention, a heat source device that generates heat, a pump that applies pressure to the circulating fluid that carries the heat generated by the heat source device, and a heat storage heat exchanger that dissipates the heat carried by the circulating fluid are connected by piping. A hot water supply heat exchanger that stores heat from the heat storage heat exchanger, including a heat storage heat exchanger, a hot water supply heat exchanger through which the supply water related to hot water supply passes, and a polymer and water. It is provided with a heat storage tank for accommodating a heat storage material that dissipates heat to the supply water passing through the water heater, and a water supply pipe serving as a flow path through which the supply water passes.

According to the present invention, the heat storage tank accommodates a heat storage material containing a polymer and water. The heat storage material 33 has a high heat storage amount corresponding to a change in the hydrogen bonding force of water when the polymer swells or contracts. As a result, it is possible to store the same amount of heat with a small capacity as compared with the case where heat is stored only in water in the heat storage tank. Therefore, the amount of heat storage and the amount of heat radiation per volume of the heat storage tank can be increased.

It is a schematic diagram which shows the structure of the hot water supply heating apparatus which concerns on Embodiment 1. FIG. It is a schematic diagram which shows the structure of the hot water supply heating apparatus which concerns on Embodiment 2.

Embodiment 1.
FIG. 1 is a schematic view showing a configuration of a hot water supply / heating device according to a first embodiment. In FIG. 1, the hot water supply / heating device 100 includes a heat pump unit 200 and a heat storage unit 300. The heat pump unit 200 and the heat storage unit 300 are connected by piping on site. Further, the heat storage unit 300 is locally connected to the heating terminal device 400, the hot water supply terminal device 500, and the water supply source 600 by piping.

The hot water supply / heating device 100, which is a combination of the heat pump unit 200 and the heat storage unit 300, is functionally classified into, for example, the equipment of the heat source unit 10, the heating unit 20, the heat storage unit 30, and the hot water supply unit 40.

The heat source unit 10 has a device that serves as a heat source device that generates heat when heating and hot water supply. Equipment that serves as a heat source includes, for example, an electric heater, a gas boiler, or a heat pump device. Here, a heat pump device having a heat pump circuit and generating heat will be described. The heat pump device mounted in the heat pump unit 200 connects a compressor 11, a heating heat exchanger 12, a depressurizing device 13, and a heat absorbing heat exchanger 14 in an annular shape via a refrigerant pipe to form a heat pump circuit in which the refrigerant circulates. Configure. As the refrigerant, a natural refrigerant such as carbon dioxide or propane gas, or an HFC-based refrigerant such as R410A or R32 can be used.

The compressor 11 sucks and compresses low-temperature and low-pressure refrigerants, and discharges them in high-temperature and high-pressure states. The heat heat exchanger 12 is a heat exchanger that functions as a heat exchanger through which the refrigerant dissipates heat. The heat exchanger 12 of the first embodiment is installed in the heat pump unit 200. The heat heat exchanger 12 heats the circulating fluid by exchanging heat between the circulating fluid, which is a heat medium for transporting heat, and the refrigerant, and dissipating heat to the refrigerant. The type of heat exchanger of the heat heat exchanger 12 is not particularly limited. For example, it may be a plate heat exchanger having a plate shape in which the refrigerant and the circulating fluid flow through different laminar flows. Further, it may be a heat exchanger having a double pipe structure in which the refrigerant and the circulating fluid flow through the outer pipe and the inner pipe, respectively. Here, the circulating fluid is a liquid fluid such as water or antifreeze. Since water is cheaper than antifreeze, it is desirable to use water.

The decompression device 13 decompresses the high-pressure refrigerant and adjusts the pressure and flow rate of the refrigerant. The pressure reducing device 13 may be, for example, an electronic expansion valve or a capillary tube. The endothermic heat exchanger 14 is, for example, a fin tube type heat exchanger. The endothermic heat exchanger 14 exchanges heat between the refrigerant flowing out of the decompression device 13 and an external heat source, dissipates heat to the external heat source, and causes the refrigerant to absorb heat. Here, the endothermic heat exchanger 14 is assumed to exchange heat between the outdoor air and the refrigerant. Here, although not shown in FIG. 1, a fan that sends air to the endothermic heat exchanger 14 may be installed in the vicinity of the endothermic heat exchanger 14.

The heating unit 20 has equipment that constitutes a fluid circuit that supplies the heat generated in the heat source unit 10. The heating unit 20 has a pump 21 and a switching valve 22. The heating unit 20 is connected to the heat source device, the heat storage unit 30 and the heating terminal device 400, which will be described later, by piping, and constitutes a fluid circuit in which the circulating fluid is circulated. The fluid circuit is a circuit for supplying the heat generated in the heat source unit 10. The pump 21 applies pressure to the circulating fluid in the fluid circuit to circulate the circulating fluid, and supplies the heat generated in the heat source unit 10 to the heat storage unit 30 or the heating terminal device 400. Further, the switching valve 22 is, for example, a three-way valve. The switching valve 22 is a valve that switches whether the circulating fluid flowing out of the heating heat exchanger 12 passes through the heating terminal device 400 side or the heat storage unit 30 side. The heating terminal device 400 is a device that heats the air-conditioned space based on the heat transferred by the circulating fluid flowing through the fluid circuit. Although not particularly limited, here, it is assumed that the heating terminal device 400 is a heating radiator that dissipates heat to heat. The heating terminal device 400 may also be a floor heating device or the like.

The heat storage unit 30 stores the heat generated in the heat source unit 10 and transferred by the circulating fluid. The heat storage unit 30 includes a heat storage tank 31, a heat storage heat exchanger 32, and a heat storage material 33. The heat storage tank 31 is, for example, a container made of SUS (stainless steel) and having a substantially rectangular parallelepiped shape. The heat storage tank 31 includes a heat storage heat exchanger 32 and a heat storage material 33 inside. The heat storage heat exchanger 32 heats the heat storage material 33 by exchanging heat between the above-mentioned circulating fluid and the heat storage material 33 and dissipating heat to the circulating fluid. The heat storage heat exchanger 32 is, for example, a fin-tube heat exchanger composed of one tube and a plurality of fins. The tube of the heat storage heat exchanger 32 becomes a part of the fluid circuit, and the circulating fluid passes through the tube. The tube of the heat storage heat exchanger 32 is made of a metal such as SUS or copper. The fins of the heat storage heat exchanger 32 increase the heat transfer area so that the heat of the circulating fluid is transferred to the heat storage material 33. The fin of the heat storage heat exchanger 32 is a plate made of a metal such as SUS or aluminum and processed into a plate shape. The heat storage material 33 stores heat from the circulating fluid by heat exchange with the heat storage heat exchanger 32. Further, as will be described later, the water supplied from the hot water supply terminal device 500 (hereinafter referred to as supply water) is heated. The heat storage material 33 contains at least a polymer and water, and is, for example, a temperature-sensitive polymer gel. A polymer is a temperature-sensitive polymer that exhibits hydrophilicity and hydrophobicity depending on a specific temperature. The specific temperature is the lower critical solution temperature (LCST) with respect to water, and the polymer exhibits hydrophilicity on the lower temperature side than LCST, hydrophobicity on the higher temperature side than LCST, and borders on LCST. Therefore, hydrophilicity and hydrophobicity change reversibly.

Specific examples of the polymer in the heat storage material 33 include N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, N, N. -Dimethyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, N-methyl-Nn-propyl (meth) acrylamide, N-isopropyl-N-methyl (meth) acrylamide, N, N-diethyl (Meta) acrylamide, N-ethoxyethyl (meth) acrylamide, N-ethyl-N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-ethoxypropyl (meth) acrylamide, N-isopropoxypropyl (Meta) acrylamide, N-methoxyethoxypropyl (meth) acrylamide, N-1-methyl-2-methoxyethyl (meth) acrylamide, N-1-methoxymethylpropyl (meth) acrylamide, N- (2,2-dimethoxy) It is a high-density crosslinked product obtained by cross-linking a polymerizable monomer such as ethyl) -N-methyl (meth) acrylamide and N, N-dimethoxyethyl (meth) acrylamide with a cross-linking agent.

The water in the heat storage material 33 is preferably pure water, but it does not have to be pure water as long as it does not contain components that may deteriorate the polymer. Water is divided into bound water bound to a high-density crosslinked product of a polymer and free water excluding bound water. Since the polymer has a hydrophilic swelling structure at a temperature lower than that of LCST, the water-bonded water forms a stable high-arranged structure and enhances the hydrogen-bonding force. On the other hand, since the polymer has a hydrophobic shrinkage structure at a temperature higher than that of LCST, the water-bonded water forms an unstable low-arranged structure and weakens the hydrogen-bonding force. As a result, the heat storage material 33 can improve or reduce the hydrogen bonding force of the bound water before and after LCST. As described above, the heat storage material 33 has a high heat storage amount corresponding to the change in the hydrogen bonding force by changing the hydrogen bonding force of the bound water before and after the LCST. That is, the heat storage material 33 has a larger amount of heat storage per filling amount than water, and the filling amount of the heat storage material 33 filled in the heat storage tank 31 can be reduced. Therefore, the amount of heat storage and the amount of heat radiation per volume of the heat storage tank 31 can be increased. Then, if the amount of heat storage is the same, the heat storage tank 31 can be made smaller than the case where heat is stored only in water. The polymer of the heat storage material is particularly thermosensitive having one or more functional groups selected from the group consisting of a hydroxy group, a sulfonic acid group, an oxysulfonic acid group, a phosphoric acid group and an oxyphosphate group at the polymer terminal. Polymers are desirable. By adjusting the composition and crosslinked structure of these materials, it has been found that a temperature-sensitive polymer gel having an endothermic peak temperature in the range of 30 ° C. to 90 ° C. and a heat storage density of 300 J / g or more can be realized. .. For hot water supply and heating applications, it is preferable to use one having an endothermic peak temperature in the range of 45 ° C. or higher and 80 ° C. or lower.

The hot water supply unit 40 has a device that supplies hot water to the hot water supply terminal device 500 by using the heat stored in the heat storage unit 30. The hot water supply unit 40 has a hot water supply heat exchanger 41 and a water supply pipe 42. The water supply pipe 42 is a pipe that serves as a flow path for water used in the hot water supply terminal device 500. Here, for example, a water supply source 600 such as a water supply is connected to a hot water supply terminal device 500 to supply tap water as supply water. A hot water supply heat exchanger 41 is installed in the water supply pipe 42. The hot water supply heat exchanger 41 is installed in the heat storage tank 31 and heats the tap water by heat exchange between the tap water passing through the water supply pipe 42 and the heat storage material 33. The hot water supply heat exchanger 41 is a fin tube type heat exchanger composed of one tube and a plurality of fins, like the heat storage heat exchanger 32, for example. The water heated by the hot water supply heat exchanger 41 is sent to the hot water supply terminal device 500 side. The hot water supply terminal device 500 is a device that uses hot water, such as a shower, a washbasin, or a kitchen. Here, the tap water supplied from the water supply source 600 is allowed to flow through the water supply pipe 42 by opening the hot water supply terminal device 500, but tap water may be allowed to flow by installing a hot water supply pump or the like. ..

Here, the operation related to the heat storage of the heat storage unit 30 will be described. The heat storage operation in the heat storage material 33 in the hot water supply / heating device 100 is, for example, when the electricity charge is low such as at midnight, when the heating terminal device 400 is stopped, and when the amount of heat storage in the heat storage tank 31 decreases. To run. The heat pump device of the heat source unit 10 generates heat for heating the heat storage material 33. The pump 21 of the heating unit 20 circulates the circulating fluid in the fluid circuit. The heat generated by the heat pump device is transferred to the heat storage unit 30 by heating the circulating fluid in the fluid circuit. In this embodiment, the LCST of the polymer is assumed to be about 60 ° C.

When the circulating fluid flows through the heat storage heat exchanger 32, the heat of the circulating fluid is transferred to the heat storage material 33 in the heat storage heat exchanger 32, and the temperature of the heat storage material 33 rises. When the temperature of the water contained in the heat storage material 33 rises, the density of the water decreases and the volume increases. Here, an air layer (not shown) is formed above the heat storage material 33 inside the heat storage tank 31, and the air in the air layer is compressed by the volume integral in which the water expands. Therefore, the volume of the heat storage tank 31 can be kept substantially constant. Here, a pressure adjusting mechanism may be provided in the heat storage tank 31 so that the pressure in the heat storage tank 31 is adjusted by the pressure adjusting mechanism when water expands.

The polymer contained in the heat storage material 33 shrinks when the temperature rises and exceeds LCST. This is called a contraction process. In the shrinkage step, the water-bonded water is arranged low and the hydrogen-bonding force is reduced. As a result, the heat storage material 33 absorbs and stores hydrogen bond energy corresponding to the decrease in hydrogen bond force. Here, in the shrinking step, the water in the heat storage tank 31 is in a liquid state. The temperature of the circulating fluid that has passed through the heat storage heat exchanger 32 drops, and the circulating fluid flows out of the heat storage tank 31.

In the operation related to heat storage, the circulating fluid circulates in the fluid circuit to heat the heat storage material 33 with the heat generated in the heat source unit 10, and the temperature of the heat storage material 33 is 70 ° C., which is, for example, 10 ° C. higher than the LCST. When it rises to, the heat storage ends.

Next, the operation related to heat dissipation of the heat storage unit 30 will be described. For example, when the hot water supply terminal device 500 is opened, for example, tap water at 10 ° C. supplied from the water supply source 600 flows through the water supply pipe 42. When tap water flows through the hot water supply heat exchanger 41, the heat of the heat storage material 33 is transferred to the tap water in the hot water supply heat exchanger 41, and the temperature of the heat storage material 33 drops. When the temperature of the water contained in the heat storage material 33 decreases, the density of the water increases and the volume decreases. Here, the volume of the heat storage tank 31, the volume of the hot water supply heat exchanger 41, the area of the fins, and the heat storage so that the entire hot water supply heat exchanger 41 can come into contact with the heat storage material 33 even when the volume of water is reduced most. The filling amount of the material 33 is designed.

The polymer contained in the heat storage material 33 dissipates heat to tap water and swells when the temperature drops below LCST. This is called a swelling process. In the swelling step, the bound water of water is arranged in a high arrangement and the hydrogen bonding force is increased. The heat storage material 33 dissipates hydrogen bond energy corresponding to an increase in hydrogen bond force. Since the temperature of the heat storage material 33 at the end of heat storage was about 70 ° C., the tap water was heated and the temperature of the tap water rose to 60 ° C. to 70 ° C. When the temperature of tap water rises to 60 ° C. or higher, it is preferable to eliminate the influence of various germs contained in tap water. Here, in the swelling step, the water in the heat storage tank 31 is in a liquid state. As described above, the tap water that has passed through the hot water supply heat exchanger 41 rises in temperature, flows out of the heat storage tank 31, and is sent to the hot water supply terminal device 500.

As described above, according to the hot water supply / heating device 100 of the first embodiment, the heat storage tank 31 of the heat storage unit 30 accommodates the heat storage heat exchanger 32, the hot water supply heat exchanger 41, and the heat storage material 33. The heat storage material 33 contains at least a polymer and water, and the polymer is a temperature-sensitive polymer that exhibits hydrophilicity and hydrophobicity depending on a specific temperature. The heat storage material 33 has a high heat storage amount corresponding to a change in the hydrogen bonding force of water when the polymer swells or contracts. As a result, it is possible to store the same amount of heat with a smaller capacity as compared with the case where heat is stored only in water in the heat storage tank 31. Therefore, the amount of heat storage and the amount of heat radiation per volume of the heat storage tank 31 can be increased. Therefore, the heat storage tank 31 that occupies a large volume in the hot water supply / heating device 100 can be miniaturized. Then, the entire hot water supply / heating device 100 can be miniaturized.

Further, in the hot water supply / heating device 100 of the first embodiment, the heat heat exchanger 12 of the heat source unit 10 that generates heat to be stored in the heat storage material 33 is arranged in the heat pump unit 200. Therefore, the heat storage unit 300 can be miniaturized. Since the heat exchanger 12 is located in the heat pump unit 200 in the hot water supply / heating device 100 of the first embodiment, the heat pump unit 200 and the heat storage unit 300 are connected by a pipe through which a circulating fluid, which is a liquid, circulates. To. Since the heat pump unit 200 has a heat pump circuit, the refrigerant does not flow into the heat storage unit 300, so that the amount of refrigerant to be filled can be reduced. Then, the environment can be improved by reducing the amount of the refrigerant.

Embodiment 2.
FIG. 2 is a schematic view showing the configuration of the hot water supply / heating device according to the second embodiment. In the hot water supply / heating device 100 of the second embodiment in FIG. 2, the heating heat exchanger 12 for heating the circulating fluid is not in the heat pump unit 200 but in the heat storage unit 300 as compared with the hot water supply / heating device 100 of the first embodiment. The difference is that they are arranged in. Therefore, the heat pump unit 200 and the heat storage unit 300 are connected by a pipe through which the refrigerant passes, not by a pipe through which the circulating fluid passes.

Since the heat heat exchanger 12 is arranged in the heat storage unit 300, the heat pump unit 200 can be miniaturized. Further, the heat pump unit 200 and the heat storage unit 300 are connected by a pipe through which a refrigerant circulates. Since the refrigerant has a low freezing point, there is no risk of freezing even at the atmospheric temperature in winter. Therefore, there is no possibility that the refrigerant pipe will be damaged by freezing.

Embodiment 3.
Next, the hot water supply / heating device 100 according to the third embodiment will be described. The equipment configuration of the hot water supply / heating device 100 according to the third embodiment is the same as the configuration described in the first embodiment and the second embodiment. In the hot water supply / heating device 100 of the third embodiment, the heat storage material 33 shown below is used.

The heat storage material 33 used in the hot water supply / heating device 100 of the third embodiment has the following general formula (1).

(In the formula, R ¹ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, R ² represents a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and R ¹ and R ² may be the same or different, R ³ represents a hydrogen atom or a methyl group, X represents a covalent bond or a hydroxy group, a sulfonic acid group, an oxysulfonic acid group, a phosphorus. It represents one or more functional groups selected from the group consisting of an acid group and an oxyphosphate group, and * represents a covalent bond) and the following general formula (2).

(In the formula, * represents a covalent bond, q represents an integer of 1 to 3), and includes a structural unit represented by the above general formula (1). It is composed of a temperature-sensitive polymer gel having a crosslinked structure in which a hand and a covalent bond of a structural unit represented by the above general formula (2) are bonded.

In the heat storage material 33 of the present embodiment, the molar ratio of the structural unit represented by the general formula (1), the functional group X, and the structural unit represented by the general formula (2) is determined. It is in the range of 99: 0.5: 0.5 to 70: 23: 7, preferably in the range of 98: 1: 1 to 77: 18: 5. When the proportion of the structural unit represented by the general formula (1) is too large (the structural unit represented by the general formula (1), the functional group X, and the general formula (2) are represented. When the total of the constituent units is 100 mol%, the heat storage density becomes smaller when the ratio of the constituent units represented by the general formula (1) exceeds 99 mol%). Here, the heat storage density is the amount of heat storage per mass. When a certain amount of heat is stored, the larger the heat storage density, the smaller the filling amount to be filled in the heat storage tank 31 of the hot water supply / heating device 100, and the smaller the size of the heat storage tank 31 can be. On the other hand, when the proportion of the structural unit represented by the general formula (1) is too small (the structural unit represented by the general formula (1), the functional group X, and the general formula (2) When the total of the structural units represented is 100 mol%, LCST is not shown when the ratio of the structural units represented by the general formula (1) is less than 70 mol%). In the present specification, the molar ratio of the structural unit represented by the general formula (1), the functional group X, and the structural unit represented by the general formula (2) is the preparation of raw materials. It is a theoretical value calculated from the quantity.

In the heat storage material 33 of the present embodiment, the structural unit represented by the general formula (1), the functional group X, and the structural unit represented by the general formula (2) are combined into the molar ratio. The number of repetitions of the structural units represented by the above general formula (1) and the order in which the respective structural units are combined are not particularly limited. The number of repetitions of the structural unit represented by the general formula (1) is usually an integer in the range of 5 to 500.

In the heat storage material 33 of the present embodiment, the LCST can be set in a wide range of 5 to 80 ° C. ^{, mainly depending on the types of R 1} and R ^{2 in the general formula (1).} ^{R 1} in the general formula (1) is preferably a hydrogen atom or a methyl group from the viewpoint of further enhancing the temperature response. ^{R 2} in the general formula (1) is preferably an ethyl group, a methyl group or an isopropyl group from the viewpoint of further enhancing the temperature responsiveness. ^{Further, R 3} in the general formula (1) is preferably a hydrogen atom from the viewpoint of facilitating the production of a temperature-sensitive polymer. X in the general formula (1) is a functional group selected from the group consisting of a hydroxy group, a sulfonic acid group, an oxysulfonic acid group, a phosphoric acid group and an oxyphosphate group so as to satisfy the above-mentioned molar ratio range. Is. Among these functional groups, an oxysulfonic acid group is preferable from the viewpoint of further enhancing radical polymerizable properties. The q in the general formula (2) is preferably 1 from the viewpoint of further increasing the heat storage density. The covalent bond in the general formulas (1) and (2) may not only combine the same structural units or different types of structural units, but may also partially form a branched structure. The branch structure is not particularly limited.

As described above, according to the hot water supply / heating device 100 of the third embodiment, the heat storage material 33 housed in the heat storage tank 31 contains a temperature-sensitive polymer having a high heat storage density. Therefore, the amount of heat storage and the amount of heat radiation per volume of the heat storage tank 31 can be increased. Then, the heat storage tank 31 can be miniaturized, and the entire hot water supply / heating device 100 can be miniaturized.

Embodiment 4.
Next, the hot water supply / heating device 100 according to the fourth embodiment will be described. The equipment configuration of the hot water supply / heating device 100 according to the third embodiment is the same as the configuration described in the first embodiment and the second embodiment. In the hot water supply / heating device 100 of the fourth embodiment, the heat storage material 33 shown below is used.

The heat storage material 33 used in the hot water supply / heating device 100 of the fourth embodiment has the following general formula (1).

(In the formula, * represents a covalent bond, q represents an integer from 1 to 3) and the following general formula (3).

Or the following general formula (4)

(In the formula, R ⁴ represents a hydroxy group, a carboxyl group, a sulfonic acid group or a phosphoric acid group, R ⁵ represents a hydrogen atom or a methyl group, and X represents a covalent bond or a hydroxy group or a sulfone. Represents one or more functional groups selected from the group consisting of an acid group, an oxysulfonic acid group, a phosphoric acid group and an oxyphosphate group, * represents a covalent bond, and p represents an integer of 1 to 3). The covalent bond of the structural unit represented by the general formula (1), the covalent bond of the structural unit represented by the general formula (2), and the covalent bond of the structural unit represented by the general formula (2) and the general formula (3). ) Or a temperature-sensitive polymer gel having a crosslinked structure in which a covalent bond of a structural unit represented by the above general formula (4) is bonded.

In the heat storage material 33 of the fourth embodiment, the range of the molar ratio between the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) or the general formula (4) is set. It is 95: 5 to 20:80, preferably in the range of 85:15 to 25:75. When the ratio of the structural unit represented by the general formula (1) is too large (the structural unit represented by the general formula (1) and the configuration represented by the general formula (3) or the general formula (4). When the total with the units is 100 mol%, the heat storage density becomes smaller when the ratio of the constituent units represented by the general formula (1) exceeds 95 mol%). On the other hand, when the ratio of the structural unit represented by the general formula (1) is too small (represented by the structural unit represented by the general formula (1) and the general formula (3) or the general formula (4). When the total of the structural units is 100 mol%, LCST is not shown when the ratio of the structural units represented by the general formula (1) is less than 20 mol%).

In the heat storage material 33 of the fourth embodiment, the total of the structural units represented by the general formula (1) and the structural units represented by the general formula (3) or the general formula (4), and the functional group The range of the molar ratio of a certain X to the structural unit represented by the general formula (2) is 99: 0.5: 0.5 to 70: 23: 7, preferably 98: 1: 1 to 98: 1: 1. The range is 77:18: 5. When the ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) or the general formula (4) is too large (the configuration represented by the general formula (1)). The total of the units and the structural units represented by the general formula (3) or the general formula (4), the functional group X, and the structural units represented by the general formula (2) is 100. When the total ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) or the general formula (4) exceeds 99 mol%) , The heat storage density becomes small. On the other hand, when the ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) or the general formula (4) is too small (represented by the general formula (1)). The total of the structural units and the structural units represented by the general formula (3) or the general formula (4), the functional group X, and the total of the structural units represented by the general formula (2). Is 100 mol%, and the total ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) or the general formula (4) is less than 70 mol%. If there is), it will not show LCST. In the present specification, the total of the structural units represented by the general formula (1) and the structural units represented by the general formula (3) or the general formula (4), and the functional group X are used. The molar ratio with the structural unit represented by the above general formula (2) is a theoretical value calculated from the amount of raw materials charged.

The heat storage material 33 of the fourth embodiment is a structural unit represented by the general formula (1), a structural unit represented by the general formula (3) or the general formula (4), and a functional group. It suffices to include X and the structural unit represented by the general formula (2) within the range of the molar ratio, and the structural unit represented by the general formula (1) and the general formula (3) or The number of repetitions of the structural units represented by the general formula (4) and the order in which the respective structural units are combined are not particularly limited. The number of repetitions of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) or the general formula (4) is usually an integer in the range of 5 to 500.

In the heat storage material 33 of the fourth embodiment, the LCST is mainly composed of a structural unit represented by the general formula (1) and a structural unit represented by the general formula (3) or the general formula (4). ^{Molar ratio and types of R 1} and R ^{2 in} the general formula (1) Wide range of 5 to 80 ° C. depending on the type ^{of R 4} and R ^{5 in} the general formula (3) or the general formula (4). Can be set to a range. ^{R 1} in the general formula (1) is preferably a hydrogen atom or a methyl group from the viewpoint of further enhancing the temperature response. ^{R 2} in the general formula (1) is preferably an ethyl group, a methyl group or an isopropyl group from the viewpoint of further enhancing the temperature responsiveness. ^{Further, R 3} in the general formula (1) ^{and R 5} in the general formula (3) or the general formula (4) are hydrogen atoms from the viewpoint of facilitating the production of a temperature-sensitive polymer. It is preferable to have. X in the general formulas (1), (3) and (4) is composed of a hydroxy group, a sulfonic acid group, an oxysulfonic acid group, a phosphoric acid group and an oxyphosphate group so as to satisfy the above-mentioned molar ratio range. It is a functional group selected from the group. Among these functional groups, an oxysulfonic acid group is preferable from the viewpoint of further enhancing radical polymerizable properties. ^{R 4} in the general formulas (3) and (4) is preferably a hydroxy group or a sulfonic acid group from the viewpoint of further increasing the heat storage density. P in the general formulas (3) and (4) is preferably 1 or 2 from the viewpoint of further increasing the heat storage density. The q in the general formula (2) is preferably 1 from the viewpoint of further increasing the heat storage density.
The covalent bond in the general formulas (1) to (4) may not only combine the same structural units or different types of structural units, but may also partially form a branched structure. The branch structure is not particularly limited.

As described above, according to the hot water supply / heating device 100 of the fourth embodiment, the heat storage material 33 housed in the heat storage tank 31 contains a temperature-sensitive polymer having a high heat storage density. Therefore, the amount of heat storage and the amount of heat radiation per volume of the heat storage tank 31 can be increased. Then, the heat storage tank 31 can be miniaturized, and the entire hot water supply / heating device 100 can be miniaturized.

Embodiment 5.
Although the above-described first and second embodiments have been described as a hot water supply / heating device 100 having a heating unit 20 for heating and to which a heating terminal device 400 can be connected, the present invention is not limited to this. Absent. The hot water supply heating device can be applied as a hot water supply device to which the heating terminal device 400 is not connected or does not have the heating unit 20.

Next, the heat storage material 33 described in the first to fifth embodiments will be specifically described with reference to Examples 1 to 3. However, the heat storage material 33 is not limited to this embodiment.

[Examples 1 to 3 and Comparative Examples 1 to 5]
The aqueous raw material solution having the composition shown in Table 1 was heated from room temperature to 50 ° C. over 1 hour under a nitrogen atmosphere to obtain a temperature-sensitive polymer. Further, the obtained temperature-sensitive polymer was dried and then equilibrium-swelled with distilled water to obtain a temperature-sensitive polymer gel. Then, the temperature-sensitive polymer gel was sealed in a closed container made of aluminum, and the endothermic peak temperature and the heat storage density were measured with a differential scanning calorimeter. The measurement results are shown in Table 2.

Here, the abbreviations in Table 1 are as follows.
NIPAM: N-Isopropylacrylamide HMA: 2-Hydroxyethyl Acrylate MBA: N, N'-Methylenebisacrylamide KPS: Carium Persulfate TEMED: N, N, N', N'-Tetramethylethylenediamine

As can be seen from the results in Table 2, the temperature-sensitive polymer gels obtained in Examples 1 to 3 have a low endothermic peak temperature of 45 ° C. to 77 ° C. and a heat storage density of 512 J / g to 844 J. It was as large as / g. Therefore, the temperature-sensitive polymer gels obtained in Examples 1 to 3 can exhibit a high heat storage density of 512 J / g to 844 J / g at a low heat storage operating temperature of about 45 ° C to 80 ° C. It is a substance that can be produced. Then, the heat storage tank 31 of the hot water supply / heating device 100 having the above configuration using the temperature-sensitive polymer gels obtained in Examples 1 to 3 depends on the heat storage density as compared with the case where heat is stored only with water. As a result, it has become possible to reduce the size by about 10% to 90%.

Further, in the reversible change in hydrophilicity and hydrophobicity of the temperature-sensitive polymer gel in which the heat storage operating temperature was exhibited, the water temperature was 45 ° C. to 77 ° C., and the gel was in a liquid state. On the other hand, the temperature-sensitive polymer gels obtained in Comparative Examples 1 to 5 have a low endothermic peak temperature of 32 ° C. to 68 ° C., similar to conventional heat storage materials such as paraffin, fatty acid, and sugar alcohol. However, the heat storage density was extremely low at 31 J / g to 42 J / g.

When a temperature-sensitive polymer gel, which is a substance having an endothermic peak temperature of 45 ° C. or higher and 80 ° C. or lower, is used as the heat storage material 33, as in the temperature-sensitive polymer gels of Examples 1 to 3, a hot water supply terminal device is used. The temperature of tap water sent to 500 rises to 40 ° C to 70 ° C. Generally, the hot water supply temperature when used for a shower or the like is preferably about 40 ° C., so that the heat storage material 33 containing the temperature-sensitive polymer gel having an endothermic peak temperature of 45 ° C. to 80 ° C. is used in the hot water supply heating device 100. convenient.

In particular, when a temperature-sensitive polymer gel, which is a substance having an endothermic peak temperature of 60 ° C. or higher and 80 ° C. or lower, such as the temperature-sensitive polymer gels of Examples 2 and 3, is used as the heat storage material 33, hot water is supplied. The temperature of tap water sent to the terminal device 500 rises to 60 ° C. to 70 ° C. When the temperature of tap water rises to 60 ° C. or higher, it is preferable to eliminate the influence of germs contained in tap water. Therefore, the heat storage material 33 containing a temperature-sensitive polymer gel having a heat absorption peak temperature of 60 ° C. or higher and 80 ° C. or lower is used. , It is more convenient for the hot water supply / heating device 100.

10 heat source unit, 11 compressor, 12 heat heat exchanger, 13 decompression device, 14 heat absorption heat exchanger, 20 heating unit, 21 pump, 22 switching valve, 30 heat storage unit, 31 heat storage tank, 32 heat storage heat exchanger, 33 Heat storage material, 40 hot water supply unit, 41 hot water supply heat exchanger, 42 water supply pipe, 100 hot water supply heating device, 200 heat pump unit, 300 heat storage unit, 400 heating terminal device, 500 hot water supply terminal device, 600 water supply source.

Claims

A fluid circuit configured by connecting a heat source device that generates heat, a pump that applies pressure to the circulating fluid that conveys the heat generated by the heat source device, and a heat storage heat exchanger that dissipates the heat transferred by the circulating fluid. ,
The heat storage heat exchanger, the hot water supply heat exchanger through which the supply water related to the hot water supply passes, and the supply that contains the polymer and water, stores heat from the heat storage heat exchanger, and passes through the hot water supply heat exchanger. A heat storage tank that houses a heat storage material that dissipates heat to water,
A hot water supply / heating device including a water supply pipe that serves as a flow path through which the supply water passes.
The hot water supply / heating device according to claim 1, wherein the polymer is a temperature-sensitive polymer that exhibits hydrophilicity and hydrophobicity depending on a specific temperature.
The heat storage material is
The polymer has a crosslinked structure and has one or more functional groups selected from the group consisting of a hydroxy group, a sulfonic acid group, an oxysulfonic acid group, a phosphoric acid group and an oxyphosphate group at the molecular end and absorbs heat. The hot water supply / heating device according to claim 1, which is a temperature-sensitive polymer gel having a peak temperature in the range of 45 ° C. to 80 ° C. and a heat storage density of 300 J / g or more.
The heat storage material has the following general formula (1).

(In the formula, R 1 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, R 2 represents a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and R 1 and R 2 may be the same or different, R 3 represents a hydrogen atom or a methyl group and X represents a covalent bond or a hydroxy group, a sulfonic acid group, an oxysulfonic acid group, a phosphorus. Represents one or more functional groups selected from the group consisting of an acid group and an oxyphosphate group, and * represents a covalent bond) and a structural unit represented by.
The following general formula (2)

(In the formula, * represents a covalent bond, q represents an integer of 1 to 3), and includes a structural unit represented by.
It has a crosslinked structure in which the covalent bond of the structural unit represented by the general formula (1) and the covalent bond of the structural unit represented by the general formula (2) are bonded.
The molar ratio of the structural unit represented by the general formula (1), the functional group X, and the structural unit represented by the general formula (2) is 99: 0.5: 0.5 to The hot water supply / heating device according to claim 2, which comprises a temperature-sensitive polymer gel having a ratio of 70:23: 7.
The heat storage material has the following general formula (1).

(In the formula, R 1 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, R 2 represents a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and R 1 and R 2 may be the same or different, R 3 represents a hydrogen atom or a methyl group and X represents a covalent bond or a hydroxy group, a sulfonic acid group, an oxysulfonic acid group, a phosphorus. Represents one or more functional groups selected from the group consisting of an acid group and an oxyphosphate group, and * represents a covalent bond) and a structural unit represented by.
The following general formula (2)

(In the formula, * represents a covalent bond and q represents an integer of 1 to 3).
The following general formula (3)

Or the following general formula (4)

(In the formula, R 4 represents a hydroxy group, a carboxyl group, a sulfonic acid group or a phosphoric acid group, R 5 represents a hydrogen atom or a methyl group, and X represents a covalent bond or a hydroxy group or a sulfone. It represents one or more functional groups selected from the group consisting of an acid group, an oxysulfonic acid group, a phosphoric acid group and an oxyphosphate group, where * represents a covalent bond and p represents an integer of 1 to 3). Including the structural unit represented by
The covalent bond of the structural unit represented by the general formula (1) and the covalent bond of the structural unit represented by the general formula (2) are represented by the general formula (3) or the general formula (4). It has a cross-linked structure in which the covalent bonds of the constituent units are bonded.
The molar ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (3) or the general formula (4) is 95: 5 to 20:80.
The sum of the structural units represented by the general formula (1) and the structural units represented by the general formula (3) or the general formula (4), the functional group X, and the general formula (2). The hot water supply / heating device according to claim 2, further comprising a temperature-sensitive polymer gel having a molar ratio of 99: 0.5: 0.5 to 70: 23: 7 with the structural unit represented by.
The hot water supply / heating device according to any one of claims 2, 4, or 5, wherein the heat storage material is made of a substance having an endothermic peak temperature of 45 ° C. or higher and 80 ° C. or lower.
The heat source device is
A compressor that compresses the refrigerant and
A heating heat exchanger that heats the circulating fluid by heat exchange between the circulating fluid and the refrigerant.
A decompression device that decompresses the refrigerant and
The invention according to any one of claims 1 to 6, which is a heat pump device having a heat pump circuit for circulating the refrigerant by connecting a heat absorption heat exchanger that absorbs heat to the decompressed refrigerant by heat exchange. Hot water supply and heating system.
A heat pump unit having the compressor of the heat pump device, the heating heat exchanger, the depressurizing device, and the endothermic heat exchanger.
The hot water supply / heating device according to claim 7, wherein the pump, the heat storage tank, and the heat storage unit having the water supply pipe are connected by a pipe through which the circulating fluid of the liquid passes.
A heat pump unit having the compressor of the heat pump device, the decompression device, and the endothermic heat exchanger.
The hot water supply / heating device according to claim 7, wherein the heating heat exchanger of the heat pump device, the pump, the heat storage tank, and the heat storage unit having the water supply pipe are connected by a pipe through which the refrigerant passes.
The invention according to any one of claims 1 to 9, further comprising a switching valve in the fluid circuit for switching between passing the circulating fluid through the heating terminal device for heating and passing the circulating fluid through the heat storage heat exchanger. The hot water supply and heating device described.